Synthesis, structure and bonding in pentagonal bipyramidal cluster compounds containing a cyclo-Sn5 ring, [(CO)3MSn5M(CO)3]4− (M = Cr, Mo)
<p>In this paper, we report the synthesis and structural characterisation of two hetero-metallic clusters, [(CO)<sub>3</sub>CrSn<sub>5</sub>Cr(CO)<sub>3</sub>]<sup>4−</sup> and [(CO)<sub>3</sub>MoSn<sub>5</sub>Mo(CO)<su...
| Hoofdauteurs: | , , , |
|---|---|
| Formaat: | Journal article |
| Taal: | English |
| Gepubliceerd in: |
MDPI
2022
|
| _version_ | 1826309807365160960 |
|---|---|
| author | Mondal, S Chen, W-X Sun, Z-M McGrady, JE |
| author_facet | Mondal, S Chen, W-X Sun, Z-M McGrady, JE |
| author_sort | Mondal, S |
| collection | OXFORD |
| description | <p>In this paper, we report the synthesis and structural characterisation of two hetero-metallic clusters, [(CO)<sub>3</sub>CrSn<sub>5</sub>Cr(CO)<sub>3</sub>]<sup>4−</sup> and [(CO)<sub>3</sub>MoSn<sub>5</sub>Mo(CO)<sub>3</sub>]<sup>4−</sup>, both of which have a pentagonal bipyramidal core. The structures are similar to that of previously reported [(CO)<sub>3</sub>MoPb<sub>5</sub>Mo(CO)<sub>3</sub>]<sup>4−</sup> and our analysis of the bonding suggests that they are best formulated as containing Sn<sub>5</sub><sup>4−</sup> rings bridging two zerovalent M(CO)<sub>3</sub> fragments. The electronic structure is compared to two isolobal M2E<sub>5</sub> clusters, [CpCrP<sub>5</sub>CrCp]<sup>−</sup> and Tl<sub>7</sub><sup>7−</sup>, both of which show clear evidence for <em>trans</em>-annular bonds between the apical atoms that is not immediately obvious in the title clusters. Our analysis shows that the balance between E-E and M-M bonding is a delicate one, and shifts in the relative energies of the orbitals on the E<sub>5</sub> and M<sub>2</sub> fragments generate a continuum of bonding situations linked by the degree of localisation of the cluster LUMO.</p> |
| first_indexed | 2024-03-07T07:41:14Z |
| format | Journal article |
| id | oxford-uuid:9c6ba0af-c45d-42a6-8a48-dfb715da7edc |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T07:41:14Z |
| publishDate | 2022 |
| publisher | MDPI |
| record_format | dspace |
| spelling | oxford-uuid:9c6ba0af-c45d-42a6-8a48-dfb715da7edc2023-04-25T10:18:46ZSynthesis, structure and bonding in pentagonal bipyramidal cluster compounds containing a cyclo-Sn5 ring, [(CO)3MSn5M(CO)3]4− (M = Cr, Mo)Journal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:9c6ba0af-c45d-42a6-8a48-dfb715da7edcEnglishSymplectic ElementsMDPI 2022Mondal, SChen, W-XSun, Z-MMcGrady, JE<p>In this paper, we report the synthesis and structural characterisation of two hetero-metallic clusters, [(CO)<sub>3</sub>CrSn<sub>5</sub>Cr(CO)<sub>3</sub>]<sup>4−</sup> and [(CO)<sub>3</sub>MoSn<sub>5</sub>Mo(CO)<sub>3</sub>]<sup>4−</sup>, both of which have a pentagonal bipyramidal core. The structures are similar to that of previously reported [(CO)<sub>3</sub>MoPb<sub>5</sub>Mo(CO)<sub>3</sub>]<sup>4−</sup> and our analysis of the bonding suggests that they are best formulated as containing Sn<sub>5</sub><sup>4−</sup> rings bridging two zerovalent M(CO)<sub>3</sub> fragments. The electronic structure is compared to two isolobal M2E<sub>5</sub> clusters, [CpCrP<sub>5</sub>CrCp]<sup>−</sup> and Tl<sub>7</sub><sup>7−</sup>, both of which show clear evidence for <em>trans</em>-annular bonds between the apical atoms that is not immediately obvious in the title clusters. Our analysis shows that the balance between E-E and M-M bonding is a delicate one, and shifts in the relative energies of the orbitals on the E<sub>5</sub> and M<sub>2</sub> fragments generate a continuum of bonding situations linked by the degree of localisation of the cluster LUMO.</p> |
| spellingShingle | Mondal, S Chen, W-X Sun, Z-M McGrady, JE Synthesis, structure and bonding in pentagonal bipyramidal cluster compounds containing a cyclo-Sn5 ring, [(CO)3MSn5M(CO)3]4− (M = Cr, Mo) |
| title | Synthesis, structure and bonding in pentagonal bipyramidal cluster compounds containing a cyclo-Sn5 ring, [(CO)3MSn5M(CO)3]4− (M = Cr, Mo) |
| title_full | Synthesis, structure and bonding in pentagonal bipyramidal cluster compounds containing a cyclo-Sn5 ring, [(CO)3MSn5M(CO)3]4− (M = Cr, Mo) |
| title_fullStr | Synthesis, structure and bonding in pentagonal bipyramidal cluster compounds containing a cyclo-Sn5 ring, [(CO)3MSn5M(CO)3]4− (M = Cr, Mo) |
| title_full_unstemmed | Synthesis, structure and bonding in pentagonal bipyramidal cluster compounds containing a cyclo-Sn5 ring, [(CO)3MSn5M(CO)3]4− (M = Cr, Mo) |
| title_short | Synthesis, structure and bonding in pentagonal bipyramidal cluster compounds containing a cyclo-Sn5 ring, [(CO)3MSn5M(CO)3]4− (M = Cr, Mo) |
| title_sort | synthesis structure and bonding in pentagonal bipyramidal cluster compounds containing a cyclo sn5 ring co 3msn5m co 3 4 m cr mo |
| work_keys_str_mv | AT mondals synthesisstructureandbondinginpentagonalbipyramidalclustercompoundscontainingacyclosn5ringco3msn5mco34mcrmo AT chenwx synthesisstructureandbondinginpentagonalbipyramidalclustercompoundscontainingacyclosn5ringco3msn5mco34mcrmo AT sunzm synthesisstructureandbondinginpentagonalbipyramidalclustercompoundscontainingacyclosn5ringco3msn5mco34mcrmo AT mcgradyje synthesisstructureandbondinginpentagonalbipyramidalclustercompoundscontainingacyclosn5ringco3msn5mco34mcrmo |